US4250283A - Titanium trihalide composition - Google Patents

Titanium trihalide composition Download PDF

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US4250283A
US4250283A US05/549,301 US54930175A US4250283A US 4250283 A US4250283 A US 4250283A US 54930175 A US54930175 A US 54930175A US 4250283 A US4250283 A US 4250283A
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titanium
aluminium
component
alkyl
titanium trihalide
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Anthony D. Caunt
James F. R. Jaggard
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Imperial Chemical Industries Ltd
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Imperial Chemical Industries Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond

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  • the present invention relates to the preparation of titanium halide compounds which are suitable for use as components of an olefine polymerisation catalyst.
  • Olefine monomers such as propylene can be polymerised using catalysts comprising a transition metal compound and an organo-metallic compound.
  • the transition metal compound is usually a solid compound if crystalline propylene polymers are being prepared and typically the transition metal compound is a titanium trihalide, especially titanium trichloride.
  • Various forms of titanium trichloride can be used and these may be obtained by the reduction of titanium tetrachloride using various reducing agents such as hydrogen, titanium metal, aluminum metal, organo-aluminum compounds or organo compounds of the non-transition metals or silicon.
  • the titanium trichloride is not a pure material but includes compounds of other metals such as, for example aluminum chloride or organo-aluminium chlorides.
  • the activity and stereospecificity of the catalyst system is dependent on the form of titanium trichloride present in the catalyst.
  • a process for the preparation of a titanium trihalide wherein a titanium tetrahalide is reacted with an organo-aluminium compound to give a titanium trihalide product and this product is treated with a solution, in a liquid hydrocarbon, of an alkyl aluminium dihalide, the amount of the alkyl aluminium dihalide being from 0.1 up to 100 moles per mole of titanium trihalide present in the titanium trihalide product.
  • the amount of alkyl aluminium dihalide is from 1 up to 10, particularly from 2 up to 8 moles per mole of titanium trihalide present in the titanium trihalide product.
  • the concentration of the alkyl aluminium dihalide is conveniently in the range from 0.1 up to 5, preferably from 0.5 up to 3.5, moles of alkyl aluminium dihalide per liter of the liquid hydrocarbon.
  • the titanium tetrahalide which is reacted with the organo-aluminium compound is preferably titanium tetrachloride when the product will be a titanium trichloride containing material.
  • the organo-aluminium compound is conveniently an aluminium alkyl of the formula
  • R is an alkyl group having 1 to 18 carbon atoms
  • X is a halogen atom
  • n is a number such that 0 ⁇ n ⁇ 3.
  • n is from 1.5 up to 2.5, especially 1.5 up to 2.0.
  • the reaction between the titanium tetrahalide and the organo-aluminium compound is preferably carried out by mixing the two components, especially by adding the aluminium compound to the titanium tetrahalide, at a relatively low temperature, for example below about 20° C., very conveniently at 0° C.
  • the time of mixing of the components will be dependent on the reaction conditions and the reactants used, however, times of 30 minutes to 16 hours, preferably 2 to 10 hours, can be used.
  • the organo-aluminium compound is a dialkyl aluminium halide, or a material including a dialkyl aluminium halide
  • the alkyl aluminium dihalide can be isohexyl aluminium dichloride, isobutyl aluminium dichloride or, preferably, ethyl aluminium dichloride.
  • Contacting of the titanium trihalide with the solution of the alkyl aluminium dihalide is preferably effected by mixing at ambient temperature and heating to an elevated temperature in the range from 60° up to 120° C. for a length of time, at the elevated temperature, of from 10 minutes up to 100 hours.
  • the length of time required for the contacting will be dependent on the temperature used, less time being required at the higher temperatures.
  • the treatment of the titanium trihalide product with the solution of the alkyl aluminium dihalide produces a titanium trihalide product which can be used to give polymerisation catalysts which show improved polymerisation activity and stereospecificity compared to an untreated reaction product.
  • reaction product is treated with a complexing agent before it is treated with the solution of the alkyl aluminium dihalide.
  • a process for the preparation of a titanium trihalide wherein a titanium tetrahalide is reacted with an organo-aluminium compound to give a titanium trihalide product, the product is treated with a complexing agent and then with a solution, in a hydrocarbon liquid, of an alkyl aluminium dihalide, the amount of the alkyl aluminium dihalide being from 0.1 up to 100, preferably from 1 up to 10, moles per mole of titanium trihalide in the titanium trihalide product.
  • the separation steps each include at least one washing stage.
  • the complexing agent is one which is capable of forming complexes with one or more of the components of the titanium trihalide product.
  • Typical complexing agents are organic compounds containing one or more atoms or groups which have one or several free electron pairs capable of co-ordination with one of the constituents of the reaction product.
  • Such compounds conveniently include a non-metallic element of Group V or VI of the Periodic Table, for example ethers, thioethers, thiols, phosphines and amines. It is particularly preferred to use as complexing agents ethers, thioethers and thiols of the formulae:
  • R' and R" which may be the same or different are hydrocarbyl groups having from 1 to 15 carbon atoms.
  • the ethers especially those wherein each hydrocarbyl group is an alkyl group containing from 4 to 10 carbon atoms or particularly 4 to 6 carbon atoms, such as di-n-butyl ether or di-iso-amyl ether, give particularly useful forms of the titanium trihalide.
  • the amount of complexing agent used will be dependent on the particular compound used but, in general, for each mole of titanium trihalide which is present in the titanium trihalide product, there is used at least 0.4 moles, and preferably 0.8 moles, for example 1.0 moles of the complexing agent, but no significant improvement in the catalyst properties are achieved when using proportions in excess of 3 moles of complexing agent for each mole of titanium trihalide.
  • a titanium trichloride product is prepared by reacting together titanium tetrachloride and an organo-aluminium compound of formula
  • R is an alkyl group having 1 to 18 carbon atoms
  • X is a halogen atom
  • R"' and R 1V can be the same or different and are alkyl groups containing from 4 up to 10 carbon atoms;
  • n 1 is from 1.5 up to 2.0.
  • the titanium trihalide as prepared in accordance with the foregoing procedure is not a pure titanium trihalide but also contains other materials which may be complexed with the titanium trihalide, such other materials including aluminium halides and hydrocarbyl aluminium halides and residual amounts of the complexing agent.
  • Titanium trihalides prepared as described herein can be used together with one or more other components to give an olefine polymerisation catalyst.
  • an olefine polymerisation catalyst comprises
  • a titanium trihalide component which is the product of reacting a titanium tetrahalide with an organo-aluminium compound to give a titanium trihalide product, and treating the titanium trihalide product with a solution in a hydrocarbon liquid, of an alkyl aluminium dihalide in the proportion of from 0.1 up to 100 moles of the alkyl aluminium dihalide for each mole of titanium trihalide present in the titanium trihalide product and optionally also treating the titanium trihalide product with a complexing agent before the treatment with the solution in a hydrocarbon liquid, of an alkyl aluminium dihalide, and
  • the catalyst optionally also includes
  • the organo-metallic compound can be Mg(C 6 H 5 ) 2 or a Grignard reagent which is substantially ether free.
  • the organo-metallic compound can be a complex of an organo-aluminium compound and an organo-metallic compound of Groups IA or IIA such as lithium aluminium tetraalkyl or Mg(AlEt 4 ) 2 .
  • the organo-metallic compound is an organo-aluminium compound such as an aluminium hydrocarbyl sulphate, an aluminium hydrocarbyl oxyhydrocarbyl, or particularly a dihydrocarbyl aluminium halide or an aluminium trihydrocarbyl.
  • the hydrocarbyl group is conveniently an alkyl group such as ethyl.
  • Mixtures of organo-aluminium compounds may be used such as a mixture of an aluminium trihydrocarbyl and an aluminium dihydrocarbyl halide for example aluminium triethyl and diethyl aluminium chloride. It is preferred that the organo-compound is halogen-free and is, in particular, an aluminium trihydrocarbyl.
  • the optional component (3) of the catalyst is a Lewis Base of the type which is effective to alter the activity and/or stereospecificity of the catalyst system.
  • Lewis Bases include the amines, particularly the cyclic amines such as pyridine, quinoline, isoquinoline and alkyl substituted derivatives of these compounds; diamines such as N,N,N',N'-tetramethylethylenediamine; alkanolamines such as N,N-dimethyl-N-ethanolamine; amides; urea and thiourea and the substituted derivatives thereof such as N,N,N',N'-tetramethylurea; organo-phosphorus compounds including the phosphites, phosphates, phosphines and phosphine oxides such as triphenyl phosphine oxide, bis(dimethylamino)ethoxy phosphine oxide and hexamethylphosphoric triamide; ethers; esters; steadidimethylamin
  • Catalyst systems including Lewis Base compounds or complexes including Lewis Base compounds are disclosed, inter alia, in British Patent Specifications Nos. 803 198; 809 717; 880 998; 896 509; 920 118; 921 954; 933 236; 940 125; 966 025; 969 074; 971 248; 1 013 363; 1 049 723; 1 122 010; 1 150 845 and 1 208 815; Dutch Patent Application No. 70 15555 and German Patent Application No. 2 130 314.
  • the organo-phosphorus compounds particularly the phosphine oxide derivatives such as hexamethylphosphoric triamide are particularly useful.
  • Lewis Bases which may very conveniently be used are phosphorus compounds selected from materials of the formulae:
  • each T is independently halogen, a hydrocarbyl group, a group --NT"' 2 or --OT"', or a heterocyclic group;
  • T' is T or a group (E--Z--G);
  • T" is T' or both the T" groups which are attached to the same P atom together to form a group ##STR2##
  • T"' is a hydrocarbyl group
  • X' is --O--, -NT""-, --E(CH 2 ) m E-- or ##STR3##
  • T"" is a hydrogen atom or T"'
  • L is a bivalent hydrocarbyl radical and each L may be the same or different;
  • each E is --O--, --S-- or --NT"'-- and may be the same or different;
  • G is --OT"', --ST"', --NT"' 2 , --PT"' 2 or a heterocyclic ring system whereof the hereroatom is O, S, N or P;
  • Q is an oxygen or sulphur atom
  • Z is a bivalent hydrocarbyl radical such that E and G or E and E are separated by not more than 3 carbon atoms;
  • each a is independently zero or 1;
  • n is a positive integer
  • x is 1, 2 or 3.
  • the groups T and T" attached to a given phosphorus atom are conveniently the same.
  • compound (c) it is particularly convenient if all the groups T" are the same.
  • the groups T, T' and T" can be alkylamino groups --NT 2 "' wherein T"' is an alkyl group such as methyl or ethyl.
  • the groups T, T' and T" may be heterocyclic groups such as pyridyl, pyrrolyl, pyrrolidyl or piperidyl and may be attached to the phosphorus atom through a carbon or nitrogen atom.
  • T' or T" is a group (E--Z--G)
  • this can be a group derived from, for example an hydroxy ether; an N,N-substituted alkanolamine, an N,N,N'-substituted diamine or an N,N-substituted aminothiol group and G can be derived from a heterocyclic compound such as pyridine, quinoline, isoquinoline, etc.
  • both of the groups T" attached to the same phosphorus atom together form a group ##STR4## this can be the divalent residue from a glycol, an N-substituted aminoalcohol, an N,N'-substituted diamine or an N-substituted aminothiol.
  • a is one and the group Q is oxygen.
  • the value of each a is the same, that is both are either zero or preferably one, and similarly it is preferred that both of the groups Q are the same and are oxygen.
  • the group X' can be derived from a monoamine or an acyclic or cyclic diamine. If the group X' is of the type --NT"'(CH 2 ) m NT"'--, the group T"' is preferably a hydrocarbyl group such as methyl and m is preferably 2 or 3. If the group X' is of the type ##STR5## it is preferred that the groups L are both the same and are alkylene groups of the type --(CH 2 ) m --, particularly ethylene groups when X' is derived from piperazine. We have obtained satisfactory polymerisation systems using as the phosphorus compound (c), materials in which the group X' is
  • Phosphorus compounds of the type (a), (b) and (c) which may be used as the third component of the catalyst include compounds of the formulae I to XXVIII. ##STR7##
  • Lewis Bases which may be used include organophosphine oxide derivatives wherein at least one group attached to the phosphorus atom is a heterocyclic group containing more than 3 atoms in the ring and attached to the phosphorus atom by a carbon or heteroatom as described in our copending British Patent Application No. 7989/73.
  • the Lewis Base may be a phosphine oxide wherein the phosphorus atom is included, together with 3 other heteroatoms, in an endocyclic ring system as described in our copending British Patent Application No. 7988/73.
  • the catalyst also optionally includes a polyene, the presence of which gives a further improvement in the polymerisation characteristics of the catalyst system.
  • the polyene may be an acyclic polyene such as 3-methylheptatriene-(1,4,6) or may be a cyclic polyene such as cyclooctatriene, cyclooctatetraene or particularly cycloheptatriene or may be a derivative of such polyenes.
  • Such derivatives can be substituted with alkyl or alkoxy groups as in methylcycloheptatriene, dimethylcyclooctatetraene and methoxycycloheptatriene or may be tropylium salts, tropylium complexes, compounds of the type ##STR8## tropolone and its derivatives of the type ##STR9## or tropones of the formula ##STR10## where
  • M' is a hydrogen, halogen, or a hydrocarbyl group, particularly an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl or alkaryl group wherein the alkyl group has 1 to 20 carbon atoms or a condensed benzene ring having two carbon atoms in common with the cycloheptatriene ring;
  • M" is a monovalent group containing at least one of the elements N, S or O;
  • M"' is a hydrocarbyl group of 1 to 20 carbon atoms, halogen or M";
  • M 1V is the same as M' and/or M";
  • R V is a hydrocarbyl group having 1 to 20 carbon atoms, which may be substituted with an alkoxy- or a hydrocarbyl-amino group;
  • b and c are integers wherein b+c ⁇ 7 and usually 2 or less, particularly one;
  • d and e are integers wherein d+e ⁇ 6;
  • f is an integer wherein f ⁇ 6.
  • Tropylium salts and tropylium complexes are salts of cycloheptatriene which may be prepared by the process described in Dolk. akad. Nauk, USSR, 113, page 339 (1957). It will be appreciated that there are many derivatives of the type described including, for example methoxyethyltropylether ##STR11##
  • the proportions of the various catalyst components can be varied widely depending both on the materials used and the absolute concentrations of the components.
  • each molecular proportion of the titanium trihalide which is component (1) of the catalyst there is present at least 0.1, and preferably at least 0.5 molecular proportions of component (2), but it may be desirable to use much greater quantities of component (2) for example as many as 50 molecular proportions, or even more, for each molecular proportion of titanium trihalide.
  • component (2) for each molecular proportion of the titanium trihalide.
  • the catalyst also optionally includes from 0.01 to 10 molecular proportions of component (3), and preferably from 0.05 to 5.0, especially from 0.2 up to 2.0 molecular proportions of component (3), with the amount, in moles, of component (3) being less than the amount, in moles, of component (2).
  • the catalyst also optionally can include a polyene and the molar proportions of the polyene plus the Lewis Base should preferably, in total, be less than the molecular proportion of component (2) (the organometallic compound) which is present in the catalyst.
  • the number of molecular proportions of the polyene is conveniently in the range 0.01 up to 1.0, especially 0.05 to 0.5, for example 0.2.
  • a preferred catalyst within the present invention comprises
  • component (2) from 0.01 up to 1.0 molecular proportions for each mole of component (2) of a substituted or unsubstituted polyene which is cyclooctatriene, cyclooctatetrene or cycloheptatriene or alkyl or alkoxyl derivatives thereof, wherein the total amount, in moles, of component (3) and, if presnt, component (4) is less than the amount, in moles, of component (2) and wherein
  • R is an alkyl group having 1 to 18 carbon atoms
  • X is a halogen atom
  • R"' and R 1V can be the same or different and are alkyl groups containing 4 to 10 carbon atoms;
  • n 1 is from 1.5 up to 2.0.
  • the catalysts of the present invention are particularly suitable for the polymerisation and copolymerisation of mono- ⁇ -olefines.
  • At least one mono- ⁇ -olefine, or a mixture of at least one mono- ⁇ -olefine and ethylene is contacted with a polymerisation catalyst comprising
  • a titanium trihalide containing component which has been obtained by reacting a titanium tetrahalide with an organo-aluminum compound to give a titanium trihalide reaction product, optionally treating the titanium trihalide product with a complexing agent, and then treating the product with a solution, in a hydrocarbon liquid, of an alkyl aluminum dihalide, the amount of the alkyl aluminum dihalide being from 0.1 up to 100 moles of alkyl aluminum dihalide per mole of titanium trihalide present in the titanium trihalide product;
  • Any mono- ⁇ -olefine monomer which is capable of being polymerised using a Ziegler catalyst may be polymerised by the process of the present invention.
  • monomers which can be polymerised by the present process include butene-1, and 4-methylpentene-1 and particularly propylene.
  • the olefines may be copolymerised either together or with ethylene, and such a copolymerisation is conveniently effected using a sequential polymerisation process such as is described in British Patents Nos. 970 478; 970 479 and 1 014 944.
  • the process of the present invention can be used for the polymerisation of propylene to give a high yield of polymer relative to the amount of catalyst used and also a relatively low proportion of the undesirable soluble polymer.
  • catalysts of the "Ziegler" type are susceptible to the effects of impurities and the activity and stereospecificity of such catalysts can be affected in a detrimental manner by the presence of small quantities of impurities, particularly oxygen and polar compounds such as water and alcohol in the monomer and/or diluent when used.
  • impurities particularly oxygen and polar compounds
  • polar compounds such as water and alcohol
  • the monomers and diluents can be used in smaller proportions than the conventional Ziegler type catalyst and accordingly are more susceptible to any impurities present in the system.
  • Any suitable purification treatment can be used and the treatment can be effected in more than one stage if desired.
  • the particular purification treatment used will be dependent on the purity of the starting materials.
  • polymerisation can be carried out in the presence or absence of an inert diluent such as a suitably purified paraffinic hydrocarbon. If a diluent is not used, polymerisation can be effected in the liquid phase using excess liquid monomer as the suspension medium for catalyst and polymer product. If the monomer is used in the gaseous phase, polymerisation can be effected using any technique suitable for effecting a gas/solid reaction such as a fluidised bed reactor system.
  • an inert diluent such as a suitably purified paraffinic hydrocarbon.
  • Polymerisation may be effected either in a batch manner or on a continuous basis.
  • the catalyst components may be introduced into the polymerisation vessel separately but it may be preferred, particularly if polymerisation is being effected on a continuous basis, to mix all the catalyst components together before they are introduced into the polymerisation reactor. Alternatively, not all of the catalyst is added at the beginning of the polymerisation. Thus, a proportion of the catalyst may be added to initiate polymerisation and further quantities of one or more of the catalyst components are added at one or more times during the polymerisation. Conveniently at least 25% of each catalyst component is added to initiate polymerisation, the remaining catalyst components being added during the polymerisation.
  • titanium trihalide such as titanium trichloride
  • the polymerisation can be effected in the presence of a chain transfer agent such as hydrogen or a zinc dialkyl, in order to control the molecular weight of the product formed.
  • a chain transfer agent such as hydrogen or a zinc dialkyl
  • the residual solid was then washed six times by suspending the solid in 3 liter batches of dry, nitrogen-purged hexane and then decanting off the hexane.
  • the propylene used for the polymerisation had been purified by passing gaseous propylene in turn through a column (3 inches diameter, 3 feet length) containing 1/16 inch granules of Alcoa F1 alumina at 50°-60° C., and then through a similar column containing BTS catalyst (Cupric oxide reduced to finely divided metallic copper on a magnesium oxide support) at 40°-50° C., condensing the issue gas and passing the liquid propylene through four columns (all 3 inches dimaeter; two of 3 feet in length, two of 6 feet in length) at 25° C., each containing 1/16 inch pellets of Union Carbide 3A molecular sieves.
  • This treatment reduced the water content of the monomer from 5-10 ppm by volume to ⁇ 1 ppm by volume and the oxygen content from 1-2 ppm by volume to ⁇ 0.5 ppm by volume.
  • the level of inert compounds nitrogen, ethane, etc.
  • the level of unsaturated hydrocarbons was unchanged at ⁇ 1 ppm.
  • a polymerisation flask equipped with efficient stirrer and a water jacket was dried carefully and 500 ml of an inert hydrocarbon diluent having a boiling range of about 170°-180° C. was introduced.
  • the diluent was evacuated at 60° C., purged with nitrogen and evacuated, which treatment effectively reduced the water and oxygen contents of the diluent to below 10 ppm by weight.
  • the diluent was then saturated with propylene to one atmosphere pressure. 5 millimoles of diethyl aluminium chloride was introduced followed by 1 millimole of hexamethylphosphoric triamide and the mixture was stirred for 30 minutes. 2.5 millimoles of TiCl 3 (prepared as described) were then introduced.
  • the pressure in the reaction vessel was maintained at one atmosphere by supply of propylene from a burette. After a further 3 hours the run was terminated with 10 milliliters of isopropanol and a sample of the supernatant liquid extracted for determining the concentration of soluble polymer. The solid was filtered and washed three times with petrol ether and dried in a vacuum oven at 120° C. for an hour. The yield of solid plus calculated soluble polymer equalled within experimental error the propylene lost from the burette.
  • a titanium trichloride reaction product was obtained by the reaction between titanium tetrachloride and diethyl aluminium chloride as described in Example 1.
  • the reaction product was then treated with di-isoamyl ether by suspending the reaction product in n-hexane to give a TiCl 3 concentration of 760 millimoles/liter and di-isoamyl ether was added at room temperature to give a molar ratio TiCl 3 to di-isoamyl ethyl of 1.03.
  • the mixture was heated to 35° C. over a period of 15 minutes and maintained at this temperature for a further hour and then cooled to ambient temperature.
  • the ether treated product was filtered off and washed 5 times with 50 ml portions of n-hexane and then suspended in n-heptane. The suspension in n-heptane was stored at ambient temperature until used.
  • the ether-treated product was then heated, either in the presence or absence of a solution of ethyl aluminium dichloride containing 1.75 moles of ethyl aluminium monochloride per liter of solution, under conditions as set out in Table 2.
  • titanium trichloride was then used to polymerise propylene as described in Example 1. In some polymerisation, no Lewis Base component was present, in which case the titanium trichloride component was added immediately after the diethyl aluminium chloride had been added. Details of the polymerisation conditions and the results obtained are set out in Table 3.
  • the ether treated product used in Examples 6 to 25 was treated with different alkyl aluminium dihalide compounds.
  • the solid was then washed four times with 30 ml portions of n-heptane.
  • the titanium trichloride containing product was then used to polymerise propylene using the conditions as indicated generally for example 1 except that one liter of hydrocarbon diluent was used and the quantities of diethyl aluminium chloride and titanium trichloride were 10 mmol and 5 mmol respectively.
  • the catalyst system did not include a Lewis Base component.
  • Other details of the conditions used for the alkyl aluminium dihalide treatment and the polymerisation results are given in Table 5.

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US4473661A (en) * 1982-07-01 1984-09-25 The Firestone Tire & Rubber Company Polymerization catalyst system containing organolithium, dialkyl magnesium and/or trialkyl aluminum, and a phosphine oxide
US4476240A (en) * 1982-07-01 1984-10-09 The Firestone Tire & Rubber Company Catalyst system containing an anionic initiator based on lithium and phosphine oxide modifier
US4530984A (en) * 1982-07-01 1985-07-23 The Firestone Tire & Rubber Company Process for production of polymers having increased 1,2-microstructure
US4537939A (en) * 1982-07-01 1985-08-27 The Firestone Tire & Rubber Company Process for production of polymers having increased 1,2-microstructure
US4564605A (en) * 1983-11-23 1986-01-14 Bp Chemicals Limited Catalyst and process for polymerizing olefins
US5587440A (en) * 1993-09-27 1996-12-24 Hoechst Aktiengesellschaft Process for the preparation of ultrahigh molecular weight polyethylene having a high bulk density
CN111408412A (zh) * 2019-01-04 2020-07-14 中国石油化工股份有限公司 一种催化剂组合物、其制备方法及其在乙烯选择性二聚化合成1-丁烯的反应中的应用

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CN111408412A (zh) * 2019-01-04 2020-07-14 中国石油化工股份有限公司 一种催化剂组合物、其制备方法及其在乙烯选择性二聚化合成1-丁烯的反应中的应用

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NO750225L (en, 2012) 1975-08-13
FR2260586A1 (en, 2012) 1975-09-05
AU7783675A (en) 1976-08-05
JPS50117695A (en, 2012) 1975-09-13
AT350252B (de) 1979-05-25
SE7501502L (en, 2012) 1975-08-13
NL7501413A (nl) 1975-08-14
ATA103375A (de) 1978-10-15
DE2505302A1 (de) 1975-08-21
CA1086712A (en) 1980-09-30

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